Thermodynamic consistency in microkinetic development of surface reaction mechanisms

The foundation of microkinetic analysis over 10 years ago has drastically changed the way of parametrization of rates of surface-catalyzed reactions. In the initial stages of development, some parameters arose from experimental data whereas others were fitted to experimental data. Semiempirical and first principles quantum mechanical and statistical mechanics simulations nowadays are powerful tools in estimating kinetic parameters. However, even in best cases, some tuning of parameters is typically necessary for quantitative model predictions. During this process, parameters of reaction mechanisms may violate thermodynamics. Here we review thermodynamic constraints of reaction networks and derive expressions applicable to surface reactions. We present three examples of ethylene hydrogenation, ammonia synthesis, and hydrogen oxidation to assess the thermodynamic validity of literature mechanisms. Various methods to ensure thermodynamic consistency are discussed and demonstrated with a specific example of H...